Phosphorus containing alkyl thio methyl carboxylates

ABSTRACT

CERTAIN SUBSTITUTED PHOSPHORUS CONTAINING ALKYL THIO METHYL CARBOXYLATES OF THE FORMULA:   R2-O-P(=S)(-R1)-S-Q   IN WHICH R1 IS ALKYL OR ALKOXY, R2 IS ALKY AND Q IS:   -R2-COO-CH2-X-R4   IN WHICH: R3 IS ALKYLENE, C1-C4; X IS SULFINYL OR THIO AND R4 IS ALKYL, C1-C4; OR   -R5(-COO-CH2-X-R4)2   IN WHICH; X AND R4 ARE AS DEFINED AND R5 IS A TRIVALENT SATURATED HYDROCARBON, C1-C3; OR   -R5(-CO-N(-R6)-R7)-COO-CH2-X-R4   IN WHICH : X, R4 AND R5 ARE AS DEFINED AND R6 AND R7 ARE HYDROGEN, ALKYL C1-C6, ARYL, HALO OR CYANO SUBSTITUTED ALKYL OR ARYL, OR TETRAHYDRO FURFURYL OR WHEN R6 AND R7 ARE TAKEN TOGETHER, AN ALKYLENE, C2-C6, ETHYLENEOXYETHLENE OR ETHYLENETHIOETHYLENE GROUPS; OR   -R5(-COO-R8)-COO-CH2-X-R4   IN WHICH: X, R4 AND R5 ARE AS DEFINED AND R8 IS ALKYL C1 TO C2 OR HALOGEN, ARYL, HALOARYL SUBSTITUTED DERIVATIVES THEREOF; OR   -C(-CH2-COO-CH2-X-R4)2-COO-CH2-X-R4   IN WHICH: X AND R4 ARE AS DEFINED AND THE USE OF THESE COMPOUNDS AS INSECTICIDES AND ACARICIDES.

United States Patent 3,562,362 PHOSPHORUS CONTAINING ALKYL THIO METHYLCARBOXYLATES Charles Kezerian, Orinda, Calif., assignor t0 StaulferChemical Company, New York, N.Y., a corporation of Delaware N0 Drawing.Filed Nov. 8, 1967, Ser. No. 681,576 Int. Cl. C07f 9/16, 9/40 US. Cl.260-942 8 Claims ABSTRACT OF THE DISCLOSURE Certain substitutedphosphorus containing alkyl thio methyl carboxylates of the formula:

i -s B in which R is alkyl or alkoxy, R is alkyl and Q is:

R is alkylene, C -C X is sulfinyl or thio and R is alkyl, C -C or inwhich:

X and R are as defined and R is a trivalent saturated hydrocarbon, C -Cor in which:

X, R; and R are as defined and R and R are hydrogen, alkyl C -C aryl,halo or cyano substituted alkyl or aryl, or tetrahydro furfuryl or whenR and R are taken together, an alkylene, C -C ethyleneoxyethylene orethylenethioethylene groups; or

in which:

X, R; and R are as defined and R is alkyl C to C or halogen, aryl,haloaryl substituted derivatives thereof; or

3,562,362 Patented Feb. 9, 1971 in which:

X and R are as defined and the use of these compounds as insecticidesand acaricides.

This invention relates to certain novel phosphorus containing alkyl thiomethyl carboxylates compounds and to their uses as insecticides andacaricides.

More specifically, this invention pertains to compounds of the formula:

in which R is selected from the group consisting of alkyl having from 1to 4 carbon atoms, preferably from 1 to 2 carbon atoms; and alkoxyhaving from 1 to 4 carbon atoms, preferably from 1 to 2 carbon atoms,and most preferably ethoxy;

R is an alkyl group having from 1 to 4 carbon atoms, preferably from 1to 2 carbon atoms, and most preferably ethyl;

Q is selected from the group consisting of:

in which:

X and R are defined as above and R is a trivalent saturated hydrocarbongroup having from 1 to 3 carbon atoms, preferably from 1 to 2 carbonatoms;

in which X, R; and R are defined as above and R and R are independentlyselected from the group consisting of hydrogen; alkyl having from 1 to 6carbon atoms and aryl, preferably phenyl, substituted derivativesthereof wherein the substituents are selected from the group con sistingof halogen, preferably chloro, and cyano; and tetrahydrofurfuryl andwhen R and R are taken together, a member selected from the groupconsisting of alkylene having from 2 to 6 carbon atoms,ethyleneoxyethylene, and ethylenethioethylene; and

1-ORs (D)Rr C-OCHzXR; I!

wherein X, R; and R are defined as above and R is selected from thegroup consisting of alkyl having from 1 to 6 carbon atoms, andsubstituted derivatives therein in which said substituents are selectedfrom the group consisting of halogen, preferably chlorine, aryl,preferably phenyl, and haloaryl, preferably chlorophenyl; and

in which X and R are defined as above.

The compounds of this invention can be prepared by various processeswhich are also features of this invention. In the following formulas R RR R R R R and R are as previously defined and K is an alkali metal andHal is chloro or bromo radical, preferably chloro.

(A) Compounds of the formula:

can be prepared in two steps according to the following generalreaction:

R1 S O I L-SK HalRa( JOH Hill-CHzSR;

Compound A Compound B Compound C More specifically, in step 1, CompoundA can be reacted with Compound B and then the intermediate reactionproduct, in step 2, can be reacted with Compound C. In the alternative,Compound B can bereacted with Compound C and the intermediate reactionproduct, in a second step, can be reacted with Compound A.

(B) By another process, compounds of the formula:

in which 'R is alkylene radical having from 2 to 3 carbon atoms can beprepared in two steps by the following general reaction:

R1 H H P-SH C=C- -OH Ha1CHzSR4 RZO/ 1k; I ib Compound E Compound DCompound 0 in which R,, and R are selected from the group consisting ofmethyl provided that both R, and R can not be methyl. More specifically,in step 1, Compound E can be reacted with Compound D and theintermediate reaction product can be reacted, in step 2, with CompoundC. In the alternative, Compound C can be reacted with Compound D andthen the intermediate reaction product, in a second step, reacted withCompound (C) Compound of the formula:

can be prepared in two steps according to the following 10 generalequation:

R SI -OH Hal-CHgSR;

R ]JOH Hal-01128114 Compound A Compound F Compound C More specifically,the above reactions can be carried 20 out by reacting Compound A withCompound F, in step 1, and then reacting, in step 2, 1 mole of theintermediate reaction product thereof with 2 moles of Compound C. In thealternative, 1 mole of Compound F can be reacted with 2 moles ofCompound C and then, as a second step, the intermediate reaction productthereof can be reacted with Compound A.

(D) Alternatively, compound of the formula:

in which R is a trivalent saturated hydrocarbon group having from 2 to 3carbon atoms, can be prepared in two steps according to the followinggeneral equation:

R S i l? r \II CC0H P-SH 2(HK1CH2SR4) CCOH R20 e 0 Compound E Compound GCompound 0 (E) Compound of the formula:

R? /P-SR5\ \R1 R20 oouzsm can be prepared by the processes described inpart (C) with the exception that a compound of the formula:

II C-N Hal-R5 R COH Compound H Compound I is substituted for Compound G.Compound H and I can be prepared by well known procedures, for example,by reacting a compound of the formula:

o H H ll 0 o-o Hal-R5 O or can be prepared by the processes described inpart (C) with the exception that a compound of the formula:

i C-O-Rs Hal-R5 C-OH H 0 Compound I is substituted for Compound D; orthey can be prepared by the processes described in Part (D) with theexception that a compound of the formula:

Compound K is substituted for Compound G. Compounds I and K can beprepared by well known procedures by reacting a compound of the formula:

respectively, with an alcohol of the formula R OH (G) Compounds of theformula:

can be prepared in two steps according to the following generalequation:

0 ll HzC-C-OH Hal-C1128 R /PSK Ha1CC(O)-OH Hal-0112811; R20 HgC-COHHub-C1128 B4 Compound A Compound L Compound 0 Accordingly, Compound Acan be reacted with Compound L in a first step and then 1 mole theintermediate reaction product produced thereby reacted with 3 moles ofCompound C. In the alternative, 3 moles of Compound C can be reactedwith 1 mole of Compound L in a first step and then the intermediatereaction product produced thereby reacted with Compound A.

All the reactions set out above between Compound C with a compound orintermediate reaction product containing one or more carboxylic acidmoieties are preferably carried out in a solvent and in the presence ofan HCl or HBr acid acceptor which are well known in the art. Thereaction can proceed without heating or the reactions are exothermic,however, heating between about 50 to C. is preferable as such reducesthe reaction time.

In those reactions in which Compound A or Compound E is a reactant thereaction proceeds readily with heating between about 50 and 80 C. in asolvent.

All of the reactions set out above should be carried out under anhydrousconditions. Examples of solvents are acetone, ether, halogenatedhydrocarbons such as carbon tetrachloride, or a liquid aliphatic oraromatic hydrocarbon, such as hexane, benzene, xylenes or the like. Theaddition reactions to unsaturated compounds in some cases proceedvigorously, usually after an induction period of a few minutes. Theseaddition reactions are preferably effected initially at below about 40C., with the reaction mixture eventually being heated at about 60 C.,for several hours to insure completion of the reaction. Re actionsinvolving evolution of a hydrogen chloride or hydrogen bromide are,preferably effected in the presence of a hydrogen chloride or hydrogenbromide acceptor, such as an organic tertiary nitrogen base such aspyridine or preferably triethylamine or K CO Bases which form a salt andwater with the hydrogen chloride or bromide should not be used as waterhas a deleterous effect on the reactions.

When the reactions are complete, any precipitate formed can be filteredoff and any solvent or other volatile material removed by distillation.

The compounds of subdivision A through F of the preceeding processes canbe converted to their sulfinyl derivatives by reacting them with anoxidizing agent such as hydrogen peroxide preferably in the presence ofa solvent such as glacial acetic acid. This reaction can be carried onconveniently at room temperature with cooling. Thus as a result of thisconversion, the moiety CH SR of these compounds is oxidized to themoiety.

The compounds of this invention can be prepared in accordance with theteaching of the following illustrative examples:

EXAMPLE I Methylthiomethyl, 2-(0,0 diethyl phosphorodithio) l-methylpropionate Call 5O S CH3 \il I II PSCHzCHC-OCH2SCH3 41.3 g. (0.135 M) ofB(0,0' diethylphosphorodithio) 1 methyl propionic acid and ml. acetonewas treated 7 with 13.5 g. (0.14 M) monochlorodimethyl sulfide. Whilestirring at 20 C., 13.6 g. (0.135 M) triethylamine was added and themixture stirred for 30 minutes, then refluxed 30 minutes. Benzene 200ml. was added with suffi cient water to separate the organic layer. Thiswas Washed with 5% HaHCO then water, dried over anhydrous magnesiumsulfate, then distilled under vacus to remove solvent and volatile.There was obtained 31 g. of yellow oil with an N of 1.5160 and infra redspectra corresponds to the above structure.

EXAMPLE II Bis methylthiomethyl, a. (0,0" diethylphophorodithio)succinate CzHsQ S \II II P-SCHGOCH2SCH2 CzH50 CH2(" o CH2SCH3 11.8 g.(0.05 M.) of his methylthiomethyl maleate and 12 g. (0.065 M) 0,0diethylphosphoro dithioic acid and a trace of hydroquinone were heatedto 6065 C. for 16 hours. The mixture was diluted with 100 ml. benzeneand washed with HaHCO solution, then with water. The organic layer wasdried over anhydrous magnesium sulfate, then distilled under vacuo toremove solvent and volatiles. There was obtained 17 g. of a yellow oilhaving an N of 1.5344. Infrared spectra of the sample corresponds to theabove structure.

Calcd. for C H O PS (percent): C, 34.2; H, 5.46; P, 7.32. Found(percent): C, 33.71; H, 5.74; P, 8.62.

EXAMPLE III N,N dimethyl, methylthiomethyl, cc (0,0diethylphosphorodithio) succinamate CzHsO EXAMPLE IV N,N dimethyl,methyl sulfinylmethyha (0,0 diethylphosphorodithio) succinamate 30 g.(0.08 mole) N,N diemethyl, methylthiomethyl,

on (0,0 diethylphosphorodithio) succinamate in 100 ml. glacial aceticacid was treated dropwise over 1 hour with 9 ml. (0.08 mole) H 0 keepingat room temperature with cooling. Stir overnight at room temperature.Benzene 300 ml. and water 500 ml. were added. Separate the organic layerand wash with water till the washings are neutral, then dried overanhydrous 25 Mg-SO, filtered and distilled under vacuum to removesolvent and volatile. A low yield 12 g. of yellow oil was obtained N1.5248. Infrared corresponds to the above structure, with a strongsulfoxide bond at 10.90 cmr EXAMPLE V Ethyl, methylthiomethyl, on (0,0dimethylphosphorodithio) succinamate CHaO S \II II /PSCHC0-CzH CHuO CHz-I:I1CCH2SCH 13 g. (0.063 M) of ethyl, methylthiomethyl maleate and 11 g.(0.07 M) of 0,0 dimethylphophorodithioic acid were mixed with 100 ml.benzene and stored for 2 days. The mixture was washed with 5% HaHCOsolution, then with water. The organic solution was dried over anhydrousmagnesium sulfate and distilled under vacus to remove solvent andvolitiles. There was obtained 12.5 g. of a yellow oil, with an N of1.5169. Infrared spectra corresponds to the above structure.

Calc. for C H O PS (percent): P, 8.55 S, 26.5. Found (percent): P, 8.24;S, 26.77.

Table I through Table V contains other compounds of this invention thatcan be prepared by the procedures described in Examples I-V.

No'rn.a, prepared in Example 1.

TABLE H 1 R1 S O-OCH2XR P-S-R R 0 fi3-OCH2XR4 R1 R2 R5 X R; 1113Compound Number:

613 Ethoxy-.. Ethy1 (|3H S Methyl 1. 5344 7 Methoxy" MethyL. CH SMethyL. 115580 NOTE.b, prepared in Example 11.

lSR R1 R20 lC|-OOH XR1 R R2 R5 X R4 6 R1 mp Compound Number:

8 Ethoxy. EthyL -GH S Methyl" Methyl V. Methyl 1.5250

g) 96, ..do "do" Same S ...de .do .d0 1.5248

10 ..do do "do S do n'Butyl nButyl 1,5110

11 -.do do d0 S d0 -.do "do ,1 1.5120

12 1o do "do S d0 Ulla-CH 1.5305

0 'l 13 d0 .do do S .d0... II2CH2 1.5316

\ /CH2 GET-CH2 14 do do .do S .do. Methyl Phenyl 1. 551g GET-CH2 17 (1o..do .do S .do Hydrogen t-Butyl 1. 5164 (T) 18 "do "do .410 S d0 CHCH 153gg O CH2-CH2 19 ...do 10 .410 S d0..... -CH.' l Hz CH2 1.5271

CHz-CEB O T 20 1o ..d0 do S -..d0....-

-CH(3H CH: GET-CH d0-.- CH2CH2-C2H4OCH3 OH2CH C2H OCH 1.5126 d0Cyclohexyl Cyanoethyl 1.5269 .d0 do "do 1.5318

NOTIL-C, prepared in Example III; (1, prepared in Example IV.

TABLE IV ll R1 S C-O-Rs \ll /PSRs R C-OCH2XR4 R1 R1 R5 X R4 R8 DDBDCompound Number:

o Methoxy.. MethyL. (3112- S MethyL. Ethyl 26 Ethoxy.-. Ethyl... R m Sdo do 1. 5120 i 27 do (in (|)Hg S d0 d0 1.5195

28 do do Same S .-do CH2CHzC1 1.5213 29.... do .....do fl S do Phenyl.1.5409

g '10 rln (in do S rln fin 1,5456

31 do do rln S fi 4-ehlorophenyl 1. 5486 0 32 (in rln dn g fln do 1.5517

NOTE.e, prepared in Example V.

TABLE v amount of Sponto 221, an emulsifying agent. The solution wasapplied as a spray to the infested plants. Con- 0 5 centratrons rangedfrom 0.05 percent downward until an R1\|S| CH2- OGHXR4 LD value wasachieved. These results are given in Table P-s-o-o o -oon2XR. II underthe column BA.

Acaricidal evaluation test.The two-spotted mite 3- R20 O OHzXR r (28M),Tetranychus telarzous (L1nn.), was employed in 0 tests for miticides.Young pinto bean plants in the pri- X so mary leaf stage were used asthe host plants. The young Compound number: pinto bean plants wereinfested with several hundred 33 Ethoxy- Ethyls Methyl mites.Dispersions of candidate materials were prepared by dissolving 0.1 gramin 10 ml. of a suitable solvent,

As previously stated the compounds of this invention are useful asinsecticides, especially systemic type insecticides.

Insecticidal evaluation test.The housefly (HF) Musca domestica (Linn.)was subjected to evaluation tests for insecticides incorporating thecompounds of the present invention.

Twenty-five female flies, three to five days old, were caged in acardboard maliing tubes 3%" in diameter 2 /6 tall. The cages weresupplied with cellophane bottoms and coarse mesh nylon tops. Each cagewas provided with food and Water. The candidate toxicant was dissolvedin a volatile solvent, preferably acetone. The solution was pippettedinto a Petri dish bottom, allowed to air dry and placed in a cardboardmailing tube cage. The flies were continuously exposed to the knownresidue of the active compound in the cage. After twenty-four andforty-eight hours, counts were made to determine living and deadinsects. The LD50 values were calculated using well known procedures.The results of this insecticidal evaluation test is given in Table IIunder HF. The Lygus bug (LB) Lygus hesperus was treated similarly as thehousefiies, except ten to twenty-five insects were used per cage. Thecaged insects were sprayed with the candidate compounds at variousconcentrations. After twenty-four and seventy-two hours, counts weremade to determine living and dead insects. The LD-SO (percent) valueswere calculated. These values are reported under the column LB in TableII.

The insect species bean aphid (BA)---Aphis fabaewas also employed in thetest for insecticidal activity. Young nasturtium plants were used as thehost plants for the bean aphid. The host plant was infested withapproximately 50 of the aphids. The test chemical was dissolved inacetone, added to water which contained a small usually acetone.Aliquots of the toxicant solutions were suspended in water containing0.0175% =v./v. Sponto 221, polyoxy-ethylene ether sorbitan monolaurate,an emulsifying agent, the amount of water being sufficient to giveconcentrations of active ingredient ranging from 0.25% to 0.0008% Thetest suspensions were then sprayed on the infested pinto bean plants.After seven days, mortalities of post-embryonic and ovicidal forms weredetermined .The percentage of kill was determined by comparison withcontrol plants which had not been sprayed with the candidate compounds.The LD-50 value was calculated using well-known procedures. These valuesare reported under the columns ZSM-PE and ZSM-Eggs in Table VI.

Systemic evaluation test.-This test evaluates the root absorption andupward translocation of the candidate systemic compound. The two-spottedmite (28M), Tetracyshus telarious (Linn.) and the bean aphid (BA), Aphisfabae, were employed in the test for systemic activity.

Young pinto bean plants in the primary leaf stage were used as hostplants for the two-spotted mite. The pinto bean plants were placed inbottles containing 200 ml. of the test solution and held in place withcotton plugs. Only the roots were immersed. The test solutions wereprepared by dissolving the compounds to be tested in a suitable solvent,usually acetone, and then diluting with distilled water. The finalacetone concentration never exceeded about 1 percent. The toxicants wereinitially tested at a concentration of 10 parts per million (ppm).Immediately after the host plant was placed in the test solution it wasinfested with the test species. Mortalities were determined after sevendays.

Young nasturtium plants were used as the host plants for the bean aphid.The host plants were transplanted into one pound of soil that had beentreated with the 14 I claim: 1. A compound of the formula:

S-Q. B20

in which:

R is selected from the group consisting of an alkyl having from 1 to 4carbon atoms and alkoxy having from 1 10 to 4 carbon atoms;

TABLE VI HF LB, BA, BAsym, E, Eggs, Systemic gram percent percent ppm.percent percent ppm.

Compound Number:

30 .003 .003 1 .003 .03 0.5 30 003 .030 3 .003 0. 5 30 .005 .003 0.3.001 .003 0.3 30 .030 .030 3 .001 .005 3 .005 .050 3 .001 .01 1 10 .001.003 0.3 .001 .003 0.1 30 .003 0. 3 .0003 .03 0. 3 20 005 0005 0. 3 003.003 0. 5 010 003 3 003 003 0. 5 50 .030 003 3 005 030 0. 3 50 .050 .00310 003 .050 3 30 050 .003 1 .003 .030 0.3 30 050 003 1 003 030 1 30 003005 3 001 030 0. 3 50 05o 003 1 005 030 1 30 .003 .003 0.3 .003 .003 0.330 030 003 1 005 030 0. s 3 .003 .003 0.3 .001 .003 0.5 50 030 003 3 003003 1 30 .010 003 3 003 003 0. 3 50 .010 .005 0.3 .003 .003 0.3 30 030 3.003 .003 1 30 .003 0. 3 30 005 3 .003 030 0. 3 50 003 003 3 005 03 3003 003 3 005 003 0. 5 030 003 3 005 030 3 20 .010 003 0. 3 .005 .0030.4 30 050 00s 1 003 003 0. 3 30 010 003 1 003 003 0. 3 50 050 003 3 003003 0. 3 30 030 003 3 003 003 0. 3

1 Not tested.

As those in the art are well aware, various techniques R is an alkylgroup having from 1 to 4 carbon atoms; are available for incorporatingthe active component or Q is a radical selected from the groupconsisting of: toxicant in suitable pesticidal compositions. Thus,pest1- (A) cidal compositions can be conveniently prepared in the H formof liquids or solids, the latter preferably as homoin which, geneousfree-flowing dusts commonly formulated by admixing the active componentwith finely divided solids or 18 an alkeylene group having from 1 to 4carbon carriers as exemplified by talc, natural clasy, diatomas; ceousearth, various flours such as walnut shell, wheat, X 15 Selected fromthe group Consisting of thiO and soya bean, cottonseed and so forth. lfand Liquid compositions are also useful and normally com- 4 15 an yl grp avlng from 1 to 4 carbon atoms; prise a dispersion of the toXicant ina liquid media, aland though it may be convenient to dissolve thetoxicant di- (13) O rectly in a solvent such as kerosene, fuel oil,Xylene, al- (Loam; XR kylated naphthalenes or the like and use suchorganic 2 4 solutions directly. However, the more common procedure is toemploy dispersions of the toxicant in an aqueous CAFCHEXR, media andsuch compositions may be produced by forrnl ing a concentrated solutionof the toxicant in a suitable in which,

organic solvent followed by dispersion in Water, usually with the aid ofsurface active agents. The latter, which may be the anionic, cationic ornonionic types, are exemplified by sodium stearate, potassium oleate andother alkaline metal soaps and detergents such as sodium lauryl sulfate,sodium naphthlene sulfonate, sodium alkyl naphthlanee sulfonate, methylcellulose, fatty alcohol ethers, polyglycol fatty acid esters and otherpolyoxyethylene surface active agents. The proportion of these agentscommonly comprises 1-15 by weight of the pesticidal compositionsalthough the proportion is not critical and may be varied to suit anyparticular situation.

X and R are defined as above and in which X, R; and R are defined asabove and R and R are independently selected from the group consistingof hydrogen; alkyl having from 1 to 6 carbon atoms and phenyl, andsubstituted derivatives thereof wherein the substituent is selected fromthe group consisting of chloro and cyano; and H wherein X, R and R aredefined as above and R is selected from the group consisting of alkylhaving from 1 to 6 carbon atoms and substituted derivatives thereof inwhich said substituents are selected from the group consisting ofchlorine, phenyl and chlorophenyl; and

in which X and R are as defined.

2. The compound of claim 1 in which Q is the radical of subdivision (A).

3. The compound of claim 1 in which Q is the radical of subdivision (B).

4. The compound of claim 1 in which Q is the radical of subdivision (C).

5'. The compound of claim 1 in which Q is the radical of subdivision(D).

16 6. The compound of claim 1 in which Q is the radical of subdivision(E).

7. The compound of claim 3 in which R is ethoxy, R is ethyl, R ismethyl, X is thio and R is 8. The compound of claim 3 in which R ismethoxy, 10 R is methyl, R is methyl, X is thio and R is H .C 11! HReferences Cited UNITED STATES PATENTS 2,831,014 4/1958 Sallmann et al260941 3,047,459 7/1962 Perini et a1. 260941X 3,134,801 5/1964 Sehringet al. 260941X 3,283,038 11/1966 Lorenz e161. 260942 3,306,898 2/1967Sehring 61131. 260941X FOREIGN PATENTS 924,657 5/1963 Great Britain260942 CHARLES B. PARKER, Primary Examiner R. L. RAYMOND, AssistantExaminer Us. 01. X.R.

" UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 562,362 Dated February 9 1971 Inventor) Charles Kezerian It is certifiedthat error appears in the above-identified. patent and that said LettersPatent are hereby corrected as shown below:

Column 3, between lines 15 and 24, the portion of the formula readingHC- H should read H a V--- (E) -q- HC- H Column 3, between lines 52 and59, the portion of the formula reading R]\ S R 0 should read S R 0Column 4, between lines 1 and 5, the portion of ti formula reading I: Iu' should read 0 ll c-o-cm sR 0- UNITED STATES PATENT OFFICE CERTIFICATEOF CORRECTION Patent No. 3, 562 ,362 D t d February 9, 1971 Inventor(s)Charles Kezerian PAGE 2 It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

r. Column 4, between lines 10 and 19, the portion of the formula readingH O should read Column 4, between lines 37 and 44, the portion 01 l llshould read Column 4, between lines 60 and 65, the portion 01 theformula reading COCH SR should read COCH SR my UNITED STATES PATENTOFFICE CERTIFICATE OF CORRECTION Patent No. 3,562,362 Dated February 9,1971 Inventofls) Charles Kezerian PAGE 3 It is certified that errorappears in the above-identified patent and that said Letters Patent arehereby corrected as shown below:

Column 5, line 44, the words "Compound I" should read ---Compound J--Column 7; line 13, the portion of the title reading "(0,0"diethylphophorodithio)" should read ---(0,0' diethylphosphorodithio)--.

Column 7, between lines 15 and 19, the portion 01 the formula reading HCH II n CH should read Column 7, between lines 40 and 42, the portion 01the formula reading I! C II n 2 n O 0 should read 2 Column 7, line 51,the word "ad", should read ---and---.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,562L362 Dated February 9 1971 Inventods) Charles Kezerian PAGE It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 8, line 17,

the word "diemethyl" should read ---dimethyl---.

Column 8, line 32, the word "succinamate" should succinamate Column 8,Between lines 32 and 40, the portion 0 the formula reading 2 2 3 readshould read Column 8, line 40, the word "dimethylphophorodit should read---dimethylphosphorodithioic---.

Column 8, in Table I, for Compound No. he, under column heading 30insert ---l.5l60---. D 7

Column 9, in Table II, the portion of the formul reading r H should readPatent No.

Inventor(s) UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION3,562,362 Dated February 9, 1971 Charles Kezerian PAGE 5 It is certifiedthat error appears in the above-identified patent and that said LettersPatent are hereby Corrected as shown below:

Column 9, immediately following Table II, insert ---TABLE III---.

Column 9, in Table III, the portion of the 01 reading ll 0 R I! 2 R C-NC-O-CH XR 2 1 0 should read c-o-ca XR vColumn 9, in Table III, forCompound No. 23, u the heading R which reads "do", insert---cyanoethyl-- Column 9, in Table III, for Compound No. 24, u theheading R which reads "do", insert ---cyc1ohexy1-- Column 11, line 49,the word "maliing" should read --mailing--.

Column 11 line 50, the figures reading "2-5/6 should read ---2-5/---. 1

Column 14, line 8, the word "an" should be de] PG-WSO UNITED STA'IESPATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 562,362 DatedFebruary 9, 1971 P Inventor(s) Charles Kezerian AGE 6 It is certifiedthat error appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

Column 1h, between lines 66 and 76 the portion of the formula reading Z4 u should read C-O-CH XR Column 15, between lines 5 and 10, the portionof the formula reading H should read -Rg Signed and sealed this 15th dayof February. 1972.

(SEAL) EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting OfficerCommissionenoi Patents

